Use of selected ester oils in drilling fluids and muds

ABSTRACT

Invert emulsion muds for drilling of gas and oil, which are environmentally safe, and which contain: 
     A. a continuous oil phase composed predominantly of at least one monocarboxylic acid ester of a C 2  -C 12  monofunctional alkalol wherein the monocarboxylic acid contains from 16 to 24 carbon atoms and is olefinically mono- or poly-unsaturated, 
     B. a disperse aqueous phase, 
     C. at least one emulsifier, 
     D. at least one weighing agent, 
     E. at least one fluid loss additive, and 
     F. a mild alkaline reserve.

This application is a continuation of U.S. application Ser. No.07/452,457 filed on Dec. 18, 1989 now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to new drilling fluids based on ester oils and toinvert drilling muds based thereon which combine high ecologicalcompatibility with good stability and performance properties.

2. State of Related Art

It is known that liquid drilling fluids for sinking bores in rock andbringing up the rock cuttings are slightly thickened, water-based oroil-based fluid systems. Oil-based systems are being increasingly usedin practice, particularly in offshore drilling or in the penetration ofwater-sensitive layers.

Oil-based drilling fluids are generally used in the form of so-calledinvert emulsion muds which consist of a three-phase system, namely: oil,water and finely divided additives, including in particular emulsifiersand emulsifier systems, weighting agents, fluid loss additives, alkalireserves, viscosity regulators and the like, for stabilizing the systemas a whole and for establishing the desired performance properties. Fullparticulars can be found, for example, in the Article by P. A. Boyd etal entitled "New Base Oil Used in Low-Toxicity Oil Muds" in the Journalof Petroleum Technology, 1985, 137 to 142 and in the Article by R. B.Bennet entitled "New Drilling Fluid Technology--Mineral Oil Mud" inJournal of Petroleum Technology, 1984, 975 to 981 and the literaturecited therein.

Oil-based drilling fluids were originally made from diesel oil fractionscontaining aromatic constituents. For the purposes of detoxification andreducing the ecological problems thus created, it was then proposed touse hydrocarbon fractions substantially free from aromaticcompounds--now also known as "nonpolluting oils"--as the continuous oilphase, cf. the literature cited above. Although certain advances wereachieved in this way through elimination of the aromatic compounds, afurther reduction in the environmental problems caused by drillingfluids of the above type seems to be urgently required. This applies inparticular to the sinking of offshore wells for the development of oiland gas sources because the marine ecosystem is particularly sensitiveto the introduction of toxic and non-readily degradable substances.

The relevant technology has for some time recognized the significance ofester-based oil pleases for solving these problems. Thus, U.S. Pat. Nos.4,374,737 and 4,481,121 describe oil-based drilling fluids in whichnonpolluting oils are said to be used. Non-aromatic mineral oilfractions and vegetable oils of the peanut oil, soybean oil, linseedoil, corn oil and rice oil type, and even oils of animal origin, such aswhale oil, are mentioned alongside one another as nonpolluting oils ofequivalent rank. The ester oils of vegetable and animal origin mentionedhere are all triglycerides of natural fatty acids which are known to beenvironmentally safe and which, ecologically, are distinctly superior tohydrocarbon fractions, even where they have been de-aromaticized.

Interestingly, however, not one of the Examples in the US patents citedabove mentions the use of such natural ester oils in invert emulsiondrilling muds. Mineral oil fractions are used throughout as thecontinuous oil phase.

In its general descriptive part, U.S. Pat. No. 4,491,121 mentions notonly triglycerides, but also a commercial product "Arizona 208" of theArizona Chemical Company, Wayne, N.J., which is a purifiedisooctyl-monoalcohol ester of high-purity tall oil fatty acids. An esterof a monofunctional alcohol and monofunctional carboxylic acids,mentioned for the first time here, is described as equivalent totriglycerides of natural origin and/or de-aromaticized hydrocarbonfractions.

The cited US patent does not contain any reproducible Examples relatingto the use of such an ester of monofunctional components.

DESCRIPTION OF THE INVENTION

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients or reaction conditions usedherein are to be understood as modified in all instances by the term"about".

The investigations on which the present invention is based have shownthat the use of readily degradable oils of vegetable and/or animalorigin, which was considered in the prior art, is not feasible forpractical reasons. The rheologic properties of such oil phases cannot becontrolled for the wide temperature range required in practice of 0° to5° C. on the one hand up to 250° C. and higher on the other hand.

The teaching of the present invention is based on the observation thatit is in fact possible to produce oil-based invert drilling fluids basedon ester oils of high environmental compatibility which correspond intheir storage and in-use behavior to the best of the hitherto knownoil-based drilling fluids, but have the additional advantage ofincreased environmental compatibility. Two key observations in thisregard dominate the teaching according to the invention:

The triglycerides accumulating in the form of natural oils are notsuitable for the production of mineral-oil-free oil-based invertdrilling fluids, whereas the esters of monofunctional carboxylic acidswith monofunctional alcohols derived from those oils or fats aresuitable for the production of such drilling fluids. The second keyobservation is that ester oils of the present type do not in fact showthe same in-use behavior as the mineral oil fractions used hithertobased purely on hydrocarbons. In practical application, the ester oilsof monofunctional components of the invention undergo partialhydrolysis, resulting in the formation of free fatty acids. These freefatty acids react in turn with the alkaline constituents always presentin invert drilling fluids, for example with the alkali reserve used toprevent corrosion, to form the corresponding salts. However, salts ofhighly hydrophilic bases and the acids in the range of from about C₁₆ toC₂₄ commonly encountered in fats and oils of natural origin are known tobe compounds having comparatively high HLB values which lead inparticular to the formation and stabilization of o/w emulsions. Use ismade of this to a very considerable extent in the field of detergentsand cleaning preparations. However, the formation of undesirably largequantities of such o/w emulsifier systems must interfere with the w/oemulsions required for solving the problem addressed by the inventionand, hence, leads to problems. The teaching of the present invention asdescribed in the following shows how invert drilling fluids based onester oils can be effectively used in practice despite thesedifficulties inherent in the system.

In a first embodiment, therefore, the present invention relates to theuse of selected esters--flowable and pumpable at temperatures in therange of from 0° to 5° C.--of monofunctional C₂₋₁₂ alcohols (alkanols)and olefinically mono- and/or polyunsaturated C16-24 monocarboxylicacids or mixtures thereof with small quantities of other, moreespecially saturated monocarboxylic acids as the oil phase, or at leasta substantial part of the oil phase, of invert drilling muds whichcontain in a continuous oil phase a disperse aqueous phase and alsoemulsifiers, weighting agents, fluid loss additives and, if desired,other standard additives together with an alkali (alkaline) reserve,with the proviso that strong hydrophilic bases, such as alkali metalhydroxides and/or diethanolamine, are not used in significantquantities. Lime (calcium hydroxide) is often added as the alkalireserve, more especially for protection against inrushes of CO₂ and/orH₂ S into the drilling fluid and hence for protection against corrosion.An addition of lime such as this may be used as the alkali reserve inaccordance with the invention. However, it is important to ensure thatonly comparatively small quantities of this alkaline component areincorporated. In a preferred embodiment of the invention, the maximumaddition of lime is of the order of 2 lb/bbl (lime/oil mud) and is thusdistinctly below the quantities typically used in practice in oil-basedinvert drilling fluids.

In another embodiment, the invention relates to mineral-oil-free invertdrilling fluids which are suitable for the offshore development of oiland gas sources and, in a continuous oil phase based on ester oils,contain a disperse aqueous phase together with emulsifiers, weightingagents, fluid loss additives and, if desired, other standard additives.The new drilling fluids are characterized in that the oil phase consistsat least substantially of esters of monofunctional C₂₋₁₂ alcohols andolefinically mono and/or polyunsaturated C₁₆₋₂₄ monocarboxylic acids andin that the w/o emulsion is mildly alkalized and, where lime is added,this alkali reserve preferably does not exceed quantities of about 2lb/bbl (lime/oil mud). The lime content is preferably slightly belowthis limit.

The ester oils selected in accordance with the invention which areintended to form the entire continuous oil phase of the invert drillingmuds or at least a substantial part thereof (i.e. over 50% by weightthereof) are discussed first in the following.

As already stated, an important criterion lies in the choice of esterswhich may be assigned to the class of reaction products ofmonofunctional carboxylic acids with monofunctional alcohols. Inaddition, however, it is intended in accordance with the inventionexclusively or at least predominantly to use C₁₆ -C₂₄ carboxylic acidswithin this class. The carboxylic acids may be derived from unbranchedor branched hydrocarbon chains, preferably linear chains. Monocarboxylicacids of this type and of the C₁₆ to C₂₄ range and esters thereof areunsuitable as predominantly saturated hydrocarbon compounds due to theircomparatively high solidification points. Even then, however, esters ofthis type are flowable and pumpable down to temperatures of 0° to 5° C.providing an adequate level of olefinically unsaturated esterconstituents is guaranteed. In the preferred embodiment of theinvention, therefore, esters of the described type of which more than70% by weight and preferably more than 80% by weight are derived fromolefinically unsaturated C₁₆₋₂₄ carboxylic acids are used. Importantnatural starting materials are carboxylic acid mixtures which contain atleast 90% by weight olefinically unsaturated carboxylic acids in theabove C range. The unsaturated carboxylic acids may be mono- and/orpolyolefinically unsaturated. Where carboxylic acids or carboxylic acidmixtures of natural origin are used, the double ethylenic double bond inparticular and, to a lesser extent, even a triple ethylenic double bondper carboxylic acid molecule plays a role in addition to a singleethylenic double bond in the molecule. Particulars of this are given inthe following.

In conjunction with the choice of esters of monofunctional reactants inaccordance with the invention, the choice of such a comparatively highlyunsaturated carboxylic acid component in the ester oils ensures that theester oils and, ultimately, the final invert emulsions show therheologic properties required in practice, particularly at relativelylow temperatures. The comparatively highly unsaturated ester oilscontaining 16 to 24 C atoms in the monocarboxylic acid component, whichare used in accordance with the invention, have solidification points(pour point and setting point) below -10° C. and more especially below-15° C. in the preferred embodiment. Despite this high mobility at lowtemperatures, the molecular size of the ester oil prescribed inaccordance with the invention ensures that the flashpoints of the esteroils are sufficiently high, being at least 80° C., and generallyexceeding a temperature limit of approximately 100° C. Ester oils havingflashpoints above 160° C. are preferred. Ester oils of the describedtype showing high mobility, even at low temperatures, and havingflashpoints of 185° C. or higher can be produced without difficulty.

In conjunction with these high flashpoints determined by the size of themolecule, it is possible at the same time to ensure that the viscosityvalues are within the required limits. Thus, preferred ester oils of thedescribed type show a Brookfield (RVT) viscosity at a temperature of 0°to 5° C. of not more than 55 mPa.s and preferably of at most 45 mPa.s orlower. It is possible to adjust values of 30 or even higher, for examplein the range of from 20 to 25 mPa.s, at temperatures in the rangeindicated.

Among the unsaturated ester oils suitable for use in accordance with theinvention, there are two sub-classes of particular importance.

The first of these sub-classes is based on unsaturated C₁₆₋₂₄monocarboxylic acids of which no more than about 35% by weight arediolefinically and, optionally, polyolefinically unsaturated. In theircase, therefore, the content of di-and polyunsaturated carboxylic acidresidues in the ester oil is comparatively limited. Within thissub-class it is preferred that at least about 60% by weight of thecarboxylic acid residues are monoolefinically unsaturated.

In contrast to the first sub-class described above, the second sub-classof ester oils of particular significance is derived from C₁₆₋₂₄unsaturated monocarboxylic acid mixtures of which more than 45% byweight and preferably more than 55% by weight are derived fromdiolefinically and/or polyolefinically unsaturated acids within theabove C range.

The most important monoethylenically unsaturated carboxylic acids withinthe above carbon range are hexadecenoic acids (palmitoleic acid (C₁₆)),oleic acid (C₁₈), the related ricinoleic acid (C₁₈) and erucic acid(C₂₂). The most important di-unsaturated carboxylic acid within therange in question here is linoleic acid (C₁₈) while the most importanttriethylenically unsaturated carboxylic acid is linolenic acid (C₁₈).

Selected individual esters formed from an unsaturated monocarboxylicacid and a monoalcohol can be used as the ester oil in accordance withthe invention. One example of such esters are the esters of oleic acid,for example of the oleic acid isobutyl ester type. So far as therheology of the system is concerned and/or for reasons of availability,it is frequently desirable to use esters from acid mixtures. This is ofimportance so far as meeting the above-stated specifications of thetwo-classes for preferred ester oils is concerned.

As already mentioned, the first of these two sub-classes isdistinguished by the fact that its content of di-unsaturated andpolyunsaturated acids is limited and does not exceed about 35% byweight. Vegetable oils of natural origin, of which the hydrolysis ortransesterification gives mixtures of carboxylic acids or carboxylicacid esters of the type required here, are for example palm oil, peanutoil, castor oil and, in particular, rapeseed oil. Suitable rapeseed oilsare both traditional types of high erucic acid content and also the moremodern types of reduced erucic acid content and increased oleic acidcontent.

Ester oils of the first sub-class which correspond to this definitionare particularly important for the simple reason that problems possiblyarising from the lack of stability to oxidation are reduced. Inpractice, the drilling fluid is of course continuously pump-circulatedand, in the process, is brought constantly into contact with atmosphericoxygen, often over a large area and at least slightly elevatedtemperatures, for the purpose of separating out the rock cuttingsbrought up, for example by sieving.

However, carboxylic acid mixtures of the second subclass mentioned aboveare also of considerable practical significance for use in accordancewith the invention. This is attributable in part to their broadaccessibility from natural fats of animal and/or vegetable origin.Classic examples of oils which have a high content of C₁₆₋₁₈ or C₁₆₋₂₂carboxylic acids and which, at the same time, contain at least about 45%of at least diethylenically unsaturated carboxylic acids are cottonseedoil, soybean oil, sunflower oil and linseed oil. The tall oil acidsisolated during the recovery of cellulose also fall within this range.However, starting materials of the last type are generally distinguishedby more or less large additional contents of resin constituents. Atypical animal starting material for the production of correspondingcarboxylic acid mixtures is fish oil, particularly herring oil.

As already mentioned, the ester oils used in accordance with theinvention can be certain selected individual esters corresponding to theabove definition. However, mixtures of esters of correspondingmonocarboxylic acids and monoalcohols will normally be present. In thisregard, the scope of the invention encompasses above all those mixtureswhich, on the one hand, meet the viscosity requirement according to theinvention and of which, on the other hand, at least 50% comprise themonofunctional esters of the olefinically mono- and/or polyunsaturatedC₁₆₋₂₄ carboxylic acids. Ester constituents and, in particular,carboxylic acid esters or monofunctional alcohols and monofunctionalcarboxylic acids of different constitution may be present as minorconstituents of the mixture providing the mixture has the requiredproperty profile. This is important where carboxylic acid mixtures ofnatural origin are used. Natural starting materials such as thesegenerally also contain more or less large proportions of saturatedcarboxylic acids, often including linear C₁₆₋₁₈ carboxylic acids.Saturated fatty acids of this type and their esters readily give rise torheologic difficulties due to their comparatively high melting points.According to the invention, therefore, saturated C₁₆₋₁₈ is carboxylicacids preferably make up no more than 20% by weight and, in particular,no more than 10% by weight of the ester oils.

By contrast, the presence of saturated carboxylic acids containing lessthan 16 carbon atoms and, more especially, from 12 to 14 carbon atoms ismore acceptable. In small quantities, the contents of such lower, fullysaturated fatty acids often present in natural starting materials arefrequently valuable mixture components in the context of the problemaddressed by the invention. Their esters are not vulnerable to oxidationunder practical inuse conditions and their rheologic properties promotethe objective of the invention, namely to replace the pure hydrocarbonoils hitherto solely used in practice by ester oils or ester oilfractions.

The alcohol radicals or the esters or ester mixtures according to theinvention are preferably derived from straight-chain and/orbranched-chain saturated alcohols, particular significance beingattributed to alcohols containing at least 3 C atoms and, moreespecially, to alcohols containing up to about 10 C atoms. The alcoholscan also be of natural origin, in which case they have normally beenobtained from the corresponding carboxylic acids or their esters byhydrogenating reduction. However, the invention is by no means limitedto starting materials of natural origin. Both on the monoalcohol sideand on the monocarboxylic acid side, the starting materials of naturalorigin may be partly or completely replaced by corresponding componentsof synthetic origin. Typical examples of alcohols are the correspondingoxo alcohols (branched alcohols) and the linear alcohols obtained by theZiegler process. Similarly, monocarboxylic acid components present inparticular in carboxylic acid mixtures can be derived from petrochemicalsynthesis. However, the advantages of starting materials of naturalorigin lie in particular in their proven lower toxicologic values, theirready degradability and their ready accessibility. The naturaldestruction of the used oil mud ultimately required presupposes thatester oils of the type described herein be both aerobically andanaerobically degradable.

However, one important limitation is associated with the use of theseester oils in invert oil muds of the type used in the present invention.This limitation arises out of the difficulty mentioned at the beginningthat, in principle, the carboxylic acid esters are vulnerable tohydrolysis and, accordingly, have to behave differently than the purehydrocarbon oils hitherto used.

Invert drilling muds of the type used herein contain the finely disperseaqueous phase, normally together with the continuous oil phase, inquantities of from 5 to 45% by weight and preferably in quantities offrom 5 to 25% by weight. Particularly preferred is the range of 10 to25% by weight of disperse aqueous phase. This pre-condition from theconstitution of conventional drilling muds also applies to theester-based invert drilling muds of the invention. It is clear that, incontinuous practical operation, disturbances of the equilibrium canoccur in the multiphase system as a result of partial ester hydrolysis.

The situation is complicated by the fact that, in practice, drillingmuds of the present type always contain an alkali reserve. This alkalireserve is particularly important in affording protection againstcorrosion caused by unexpected inrushes of acidic gases, particularlyCO₂ and/or H₂ S. The danger of corrosion to the drill pipe requires thesafe establishment of pH values at least in the mildly alkaline range,for example in the range from pH 8.5 to 9 and higher.

In oil muds based on pure hydrocarbon fractions as the oil phase,strongly alkaline and, at the same time, highly hydrophilic inorganic ororganic additives are generally used in practice without any difficulty.Particular significance can be attributed to the alkali hydroxides and,in particular, to sodium hydroxide on the one hand or to highlyhydrophilic organic bases, diethanolamine and/or triethanolamine beingparticularly typical additives for binding impurities of H₂ S. Inaddition to and/or instead of the highly hydrophilic inorganic andorganic bases mentioned here, lime or even more weakly basic metaloxides, especially zinc oxide or comparable zinc compounds, areparticularly important as the alkali reserve. Lime in particular iswidely used an inexpensive alkalizing agent. It may safely be used incomparatively high quantities of, for example, from 5 to 10 lb/bbl(lime/oil mud) or even higher.

The use of the ester-based oil muds of the invention requires adeparture from standard practice so far as these variables areconcerned. It is of course necessary in this case, too, to ensure thatthe pH value of the drilling mud is kept at least in the mildly alkalinerange and that a sufficient quantity of alkali reserve is available forunexpected inrushes of, in particular, acidic gases. At the same time,however, the ester hydrolysis should not be undesirably promoted and/oraccelerated by such an alkali content.

Thus, in the preferred embodiment of the invention, no significantquantities of highly hydrophilic, inorganic and/or organic bases areused in the oil mud. In particular, the invention does not use alkalihydroxides or highly hydrophilic amines of the diethanolamine and/ortriethanolamine type. Lime may be effectively used as the alkalireserve. In that case, however, it is best to limit the maximum quantityof lime used in the drilling mud to around 2 lb/bbl or slightly lower,for example to between 1 and 1.8 lb/bbl (lime/drilling mud). In additionto or instead of lime, it is also possible to use other known alkalireserves, including in particular the less basic metal oxides of thezinc oxide type and other comparable zinc compounds. However, even whereacid-binding agents such as these are used, it is important not to useexcessive amounts to prevent unwanted premature ageing of the drillingmud accompanied by an increase in viscosity and hence a deterioration inthe rheologic properties. The particular aspect of the teachingaccording to the invention prevents or at least limits the formation ofunwanted quantities of highly active o/w emulsifiers to such an extentthat the favorable rheologic properties are maintained for long periodsin operation, even in the event of thermal ageing. In relation to therecommendations of the prior art which have hitherto remained in therealm of theoretical considerations, this represents a significantsurplus which actually enables the low toxic properties of ester oils ofthe present type to be utilized in practice for the first time.

The esters based on olefinically unsaturated C₁₆₋₂₄ monocarboxylic acidsdefined in accordance with the invention, which flow and can be pumpedat temperatures in the range from 0° to 5° C., generally make up atleast about half the continuous oil phase of the drilling mud. However,preferred oil phases are those in which esters or ester mixtures of thetype according to the invention are very much predominantly present. Inone particularly important embodiment of the invention, the oil phaseconsists almost entirely of such ester oils. Components suitable formixing with the ester oils defined in accordance with the invention are,in particular, selected other ester oil fractions which are described inU.S. Ser. No. 07/452,988 now abandoned "Drilling Fluids and MudsContaining Selected Ester Oils"), filed of even data herewith. Theinvention also encompasses mixtures with such other selected ester oils.These ester oils, which are described in the above copendingapplication, incorporated herein by reference, are esters ofmonofunctional C₂₋₁₂ alcohols and saturated aliphatic C₁₂₋₁₆monocarboxylic acids.

The following rheologic data apply to the rheology of preferred invertdrilling muds according to the invention: plastic viscosity (PV) in therange of from 10 to 60 mPa.s and preferably in the range of from 15 to40 mPa.s, yield point (YP) in the range of from 5 to 40 lb/100 ft² andpreferably in the range of from 10 to 25 lb/100 ft², as measured at 50°C. Full information on the determination of these parameters, on themeasurement techniques used and on the otherwise standard composition ofthe invert oil muds described herein can be found in the prior art citedabove and, for example, in "Manual of Drilling Fluids Technology"published by BAROID DRILLING FLUIDS, INC., cf. in particular the Chapterentitled "Mud Testing--Tools and Techniques" and "Oil Mud Technology",which is freely available to interested experts. In the interests offullness of disclosure, the following summary observations may be made:

Emulsifiers suitable for use in practice are systems which are capableof forming the required w/o emulsions. Selected olephilic fatty acidsalts, for example those based on amidoamine compounds, are particularlysuitable, examples being described in the already cited U.S. Pat. No.4,374,737 and the literature cited therein. One particularly suitabletype of emulsifier is the product marketed under the name of "EZ-MUL™"by BAROID DRILLING FLUIDS, INC.

Emulsifiers of the above type are marketed in the form of concentrateand can be used, for example, in quantities of from 2.5 to 5% by weightand more especially in quantities of from 3 to 4% by weight, based ineach case of the ester oil phase.

In practice, organophilic lignite is used as a fluid-loss additive andforms an impervious coating in the form of a substantiallywater-impermeable film over the walls of the well. Suitable quantitiesare, for example, in the range of from 15 to 20 lb/bbl or in the rangeof from 5 to 7% by weight, based on the ester oil phase.

In drilling muds of the present type, the thickener normally used tocreate viscosity is a cationically modified, finely divided organophilicbentonite which can be used in quantities of from 8 to 10 lb/bbl or inthe range of from 2 to 4% by weight, based on the ester oil phase. Theweighing agent normally used in practice to establish the necessarypressure equalization is barite which is added in quantities adapted tothe particular conditions to be expected in the well. For example, it ispossible by addition of barite to increase the specific gravity of thedrilling mud to values of up to about 2.5 and preferably in the rangefrom 1.3 to 1.6.

In invert drilling muds of the present type, the disperse aqueous phaseis charged with soluble salts, generally calcium chloride and/orpotassium chloride, the aqueous phase preferably being saturated withthe soluble salt at room temperature.

The emulsifiers or emulsifier systems mentioned above can also be usedto improve the oil wettability of the inorganic weighting materials. Inaddition to the aminoamides already discussed, alkyl benzensulfonatesand imidazoline components are further examples. Additional informationon the relevant prior art can be found in the following literaturereferences: GB 2,158,437, EP 229 912 and DE 32 47 123.

One important application for the new drilling fluids is in offshoredrilling for the development of oil and/or gas sources, to providetechnically useful drilling fluids of high ecological compatibility. Theuse of the new drilling fluids is of particular importance in, but isnot limited to, the offshore sector. The new drilling fluids can also beused quite generally for land-supported drilling, including for examplegeothermal drilling, water drilling, geoscientific drilling and minedrilling. In this case, too, the ester-based drilling fluids selected inaccordance with the invention basically simplify ecotoxic problems to aconsiderable extent. In addition, the drilling fluids based inaccordance with the invention on the co-use of ester oils of thedescribed type are also distinguished by distinctly improved lubricity.This is particularly important when the path of the drill pipe and hencethe well deviate from the vertical during drilling, for example atconsiderable depths. In such cases, the rotating drill pipe readilycomes into contact with the well wall and embeds itself therein. Esteroils of the type used as oil phase in accordance with the invention havea distinctly better lubricating effect than the mineral oils hithertoused, which is an important advantage of the present invention.

The invention will be illustrated but not limited by the followingexamples.

EXAMPLES EXAMPLE 1

An invert drilling mud was prepared using an undistilled isobutylrapeseed oil ester at the continuous oil phase. This rapeseed ester wasbased on a mixture of predominantly unsaturated, straight-chaincarboxylic acids which correspond substantially to the followingdistribution; 60% oleic acid, 20% linoleic acid, 9 to 10% linolenicacid, olefinically unsaturated C₂₀₋₂₂ monocarboxylic acids approximately4% remainder saturated monocarboxylic acids predominantly in the C₁₆₋₁₈range.

The rapeseed oil ester used had the following characteristic data:density (20° C.) 0.872 g/cm³ ; pour point below -15° C.; flash point(DIN 51584) above 180° C.; acid value (DGF-C-V 2) 1.2; viscosity at 0°C. 32 mPa.s, viscosity at 5° C. 24 mPa.s; no aromatic compounds.

An invert drilling mud was conventionally prepared using the followingmixture constituents:

    ______________________________________    230    ml rapeseed oil fatty acid ester    26     ml water    6      g organophilic bentonite (GELTONE ™, a product           of BAROID DRILLING FLUIDS, INC. of Aberdeen,           Scotland)    0.2    g line    6      g water in oil emulsifier ("EZ-MUL ™", a product           of BAROID DRILLING FLUIDS, INC.)    340    g basis    9.2    g CaCl.sub.2 × 2H.sub.2 O    20     g organophilic lignite ("DURATONE ™", a product           of BARIOD DRILLING FLUIDS. INC.)    ______________________________________

Plastic viscosity (PV), yield point (YP) and gel strength after 10seconds and 10 minutes were first determined on the material beforeageing by viscosity measurement at 50° C.

The invert drilling mud was then aged for 16 h at 125° C. in anautoclave in a so-called "roller oven" to determine the effect oftemperature on the stability of the emulsion. The viscosity values wereredetermined at 50° C.

The following results were obtained:

    ______________________________________                     Unaged                           Aged                     material                           material    ______________________________________    Plastic viscosity (PV)                       35      62    Yield point (YP)   21      24    Gel strength (lb/100 ft.sup.2)    10 seconds         12      12    10 minutes         14      15    ______________________________________

COMPARISON EXAMPLE 1

Another invert drilling mud was prepared in the same way as in Example1, except that on this occasion the quantity of lime was increased to 4g, i.e. drastically beyond the limit of approximately 2 lb/bbl.

Once again, the viscosity values and gel strength of the material weredetermined before and after ageing. The following results were obtained:

    ______________________________________                    Unaged                          Aged                    material                          material    ______________________________________    Plastic viscosity (PV)                      41      cannot                              be measured    Yield point (YP)  22      cannot                              be measured    Gel strength (lb/100 ft.sup.2)    10 seconds        11      74    10 minutes        17      72    ______________________________________

EXAMPLE 2

Another invert drilling mud was prepared with a continuous oil phase.The oil phase consisted of distilled oleic acid isobutyl ester which hasthe following characteristic data: density (20° C.) 0.86 gg/cm³ ;viscosity (20° C.) 8 to 10 mPa.s; pour point below -25° C.; flash point(51584) above 185° C.; acid value (DGF)-CV 2) below 1; no aromaticcompounds.

A drilling mud of the following composition was prepared:

    ______________________________________    210    ml isobutyl oleate    6      g fatty-acid-based emulsifier (INVERMUL ™, a           product of BAROID DRILLING FLUIDS, INC.)    6      g organophilic bentonite (GELTONE II ™, a product           of BAROID DRILLING FLUIDS, INC.)    13     g organophilic lignite (DURATONE ™, a product           of BAROID DRILLING FLUIDS, INC.)    1      g lime    3      g water in oil emulsifier (EZ-MUL ™, a product           of BAROID DRILLING FLUIDS, INC.)    270    g barite    58.2   g saturated aqueous CaCl.sub.2 solution    ______________________________________

Plastic viscosity, yield point and gel strength after 10 seconds and 10minutes were determined before and after ageing (16 h at 125° C. in aroller oven) in the same way as in Example 1. The results obtained areshown below. In the formulation used here, . .1.2 kg.!. .Iadd.1.9 g.Iaddend.lime substantially corresponds to the limit of 2 lb/bbl.

    ______________________________________                     Unaged                           Aged                     material                           material    ______________________________________    Plastic viscosity (PV)                       46      41    Yield point (YP)   35      32    Gel strength (lb/100 ft.sup.2)    10 seconds         17      18    10 minutes         21      29    ______________________________________

. .COMPARISON.!. EXAMPLE . .2.!. .Iadd.3 .Iaddend.

Another invert drilling oil emulsion was prepared using the formulationof Example 2, except that the addition of lime was increased to 2 g andhence to . .clearly beyond.!. .Iadd.within .Iaddend.the limit of.Iadd.about .Iaddend.2 lb/bbl. The plastic viscosity, yield point andgel strength of the material before and after ageing are shown in thefollowing:

    ______________________________________                     Unaged                           Aged                     material                           material    ______________________________________    Plastic viscosity (PV)                       33      46    Yield point (YP)   61      45    Gel strength (lb/100 ft.sup.2)    10 seconds         33      24    10 minutes         40      29    ______________________________________

We claim:
 1. An invert emulsion drilling mud free of mineral oil andsubstantially free from highly hydrophilic basic materials selected fromthe group consisting of alkali metal hydroxides and amines selected fromdiethanolamine and triethanolamine, consisting essentially ofA. acontinuous oil phase composed predominantly of at least onemonocarboxylic acid ester of a C₂ -C₁₂ monofunctional alcohol whereinthe monocarboxylic acid contains from 16 to 24 carbon atoms and isolefinically mono- or poly-unsaturated, B. a disperse aqueous phase, C.at least one emulsifier, D. at least one weighting agent, E. aviscosifier, F. at least one fluid loss additive, and G. a mildlyalkaline alkali reserve component consisting essentially of lime in aquantity not exceeding about 2 lb/bbl of said drilling mud.
 2. Theinvert emulsion mud of claim 1 wherein the disperse aqueous phase Bcontains at least one of CaCl₂ or KCl as a dissolved salt.
 3. The invertemulsion mud of claim 1 wherein from about 5 to about 45% by weight ofcomponent B is present therein.
 4. The invert emulsion mud of claim 3wherein from about 10 to about 25% by weight of component B is presenttherein.
 5. The invert emulsion mud of claim 1 wherein component A has aBrookfield (RVT) viscosity at 0° to 5° C. of below 50 mPa.s.
 6. Theinvert emulsion mud of claim 1 wherein the invert emulsion mud has aplastic viscosity (PV) in the range of from about 10 to about 60 mPa.sand a yield point (YP) in the range of from about 5 to about 40 lb/100ft², as measured at 50° C.
 7. The invert emulsion mud of claim 1 whereincomponent A also contains esters of saturated monocarboxylic acids. 8.The invert emulsion mud of claim 1 wherein in component A the oil phasecontains at least about 70% by weight of the at least one monocarboxylicacid ester.
 9. The invert emulsion mud of claim 8 wherein about 80% byweight of the at least one monocarboxylic acid ester is present.
 10. Theinvert emulsion mud of claim 8 wherein about 90% by weight of the atleast one monocarboxylic acid ester is present.
 11. The invert emulsionmud of claim 1 wherein the at least one monocarboxylic acid ester ofcomponent A has a pour point and setting point below about -10° C., anda flash point above about 100° C.
 12. The invert emulsion mud of claim11 wherein the pour point and setting point is below about -15° C., andthe flash point is above about 160° C.
 13. The invert emulsion mud ofclaim 1 wherein in component A the acid moiety of the at least onemonocarboxylic acid ester contains at least about 60% by weight ofmonoolefinically unsaturated acids and no more than about 35% by weightdi- and polyolefinically unsaturated acids.
 14. The invert emulsion mudof claim 1 wherein in component A the acid moiety of the at least onemonocarboxylic acid ester contains more than about 45% by weight ofeither diolefinically unsaturated acids, polyolefinically unsaturatedacids, or a mixture of di- and poly-olefinically unsaturated acids. 15.The invert emulsion mud or claim 14 wherein said percentage is more thanabout 55%.
 16. The invert emulsion mud of claim 1 wherein in component Athe continuous oil phase contains no more than about 20% by weight ofesters of saturated C₁₆ -C₁₈ carboxylic acids.
 17. The invert emulsionmud of claim 16 wherein said percentage is no more than about 10% byweight.
 18. The invert emulsion mud of claim 1 wherein in the at leastone monocarboxylic acid ester of component A the monocarboxylic acid islinear.
 19. The invert emulsion mud of claim 1 wherein in the at leastone monocarboxylic acid ester of component A the alcohol moiety containsfrom 3 to 10 carbon atoms and is saturated, straight chain or branched.20. The invert emulsion mud of claim 1 wherein said lime is present inan amount of from 1 to 1.8 lbs/bbl of said drilling mud.
 21. The invertemulsion mud of claim 1 wherein said alkali reserve component includes aweakly basic metal oxide, zinc oxide, or zinc compound. . .22. Theinvert emulsion mud of claim 1 wherein in component A the acid moiety ofthe at least one monocarboxylic acid ester contains more than about 45%by weight of either diolefinically unsaturated acids, polyolefinicallyunsaturated acids, or a mixture of di- and poly- olefinicallyunsaturated acids..!.23. . .A drilling fluid.!. .Iadd.An invert drillingfluid that is .Iaddend.free of mineral oil . .for use in an invertdrilling mud that.!. .Iadd.and .Iaddend.is substantially free fromhighly hydrophilic basic materials selected from the group consisting ofalkali metal hydroxides and amines selected from diethanolamine andtriethanolamine, .Iadd.said fluid .Iaddend.consisting ofA. a continuousoil phase composed of at least one monocarboxylic acid ester of a C₂-C₁₂ monofunctional alkanol wherein the monocarboxylic acid containsfrom 16 to 24 carbon atoms and comprises at least about 60% by weight ofmonoolefinically unsaturated acids and no more than about 35% by weightof di- and poly- olefinically unsaturated acids, . .and.!. B. a disperseaqueous phase. ...!. .Iadd., and C. a mildly alkaline alkali reservecomponent consisting essentially of lime in a quantity not exceedingabove about 2 lb/bbl of said drilling fluid. .Iaddend.24. The drillingfluid of claim 23 wherein in component A has a Brooksfield (RVT)viscosity at 0° to 5° C. of below 50 mPa.s.
 25. The drilling fluid ofclaim 23 wherein in component A the oil phase contains at least about70% by weight of the at least one monocarboxylic acid ester.
 26. Thedrilling fluid of claim 23 wherein the at least one monocarboxylic acidester of component A has a pour point and setting point below about -10°C., and a flash point above about 100° C.
 27. The drilling fluid ofclaim 23 wherein in the at least one monocarboxylic acid ester ofcomponent A the monocarboxylic acid is linear.
 28. The drilling fluid ofclaim 23 wherein in the at least one monocarboxylic acid ester ofcomponent A the alcohol moiety contains from 1 to 10 carbon atoms and issaturated, straight chain or branched.
 29. An invert emulsion drillingmud free of mineral oil and substantially free from highly hydrophilicbasic materials selected from the group consisting of alkali metalhydroxides and amines selected from diethanolamine and triethanolamine,consisting essentially ofA. a continuous oil phase composedpredominantly of at least one monocarboxylic acid ester of a C₂ -C₁₂monofunctional alcohol wherein the monocarboxylic acid contains from 16to 24 carbon atoms and comprises at least about 60% by weight ofmonoolefinically unsaturated acids and no more than about 35% by weightof di- and poly- olefinically unsaturated acids, B. a disperse aqueousphase, C. at least one emulsifier, D. at least one weighting agent, E. aviscosifier, F. at least one fluid loss additive, and G. a mildlyalkaline alkali reserve component consisting essentially of lime in aquantity not exceeding about 2 lb/bbl of said drilling mud.
 30. Theinvert emulsion mud of claim 29 wherein from about 5 to about 45% byweight of component B is present therein.
 31. The invert emulsion mud ofclaim 30 wherein from about 10 to about 25% by weight of component B ispresent therein.
 32. The invert emulsion mud of claim 29 whereincomponent A has a Brookfield (RVT) viscosity at 0° to 5° C. of below 50mPa.s.
 33. The invert emulsion mud of claim 29 wherein the invertemulsion mud has a plastic viscosity (PV) in the range of from about 10to about 60 mPa.s and a yield point (YP) in the range of from about 5 toabout 40 lb/100 ft², as measured at 50° C.
 34. The invert emulsion mudof claim 29 wherein in component A the oil phase contains at least about70% by weight of the at least one monocarboxylic acid ester. . Theinvert emulsion mud of claim 29 wherein the at least one monocarboxylicacid ester of component A has a pour point and setting point below about-10° C., and a flash point above about 100° C.
 36. In the development ofa source of oil or gas by drilling using a drilling mud, the improvementcomprising pumping the invert emulsion mud of claim 2 into said source.37. In the development of a source of oil or gas by drilling using adrilling mud, the improvement comprising pumping the invert emulsion mudof claim 6 into said source. In the development of a source of oil orgas by drilling using a drilling mud, the improvement comprising pumpingthe invert emulsion mud of claim 11 into said source.
 39. In thedevelopment of a source of oil or gas by drilling using a drilling mud,the improvement comprising pumping the invert emulsion mud of claim 13into said source.
 40. In the development of a source of oil or gas bydrilling using a drilling mud, the improvement comprising pumping theinvert emulsion mud of claim 1 into said source.
 41. In the developmentof a source of oil or gas by drilling using a drilling mud, theimprovement comprising pumping the invert emulsion mud of claim 29 intosaid source. .Iadd.42. The invert emulsion mud of claim 19 wherein thealcohol moiety is branched and the monocarboxylic acid is predominantlyoleic acid. .Iaddend..Iadd.43. The invert emulsion mud of claim 42wherein the monocarboxylic acid is derived from rape seed oil. .Iaddend.